EP0742806B1 - Herstellung von polyglycerol - Google Patents

Herstellung von polyglycerol Download PDF

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Publication number
EP0742806B1
EP0742806B1 EP95906988A EP95906988A EP0742806B1 EP 0742806 B1 EP0742806 B1 EP 0742806B1 EP 95906988 A EP95906988 A EP 95906988A EP 95906988 A EP95906988 A EP 95906988A EP 0742806 B1 EP0742806 B1 EP 0742806B1
Authority
EP
European Patent Office
Prior art keywords
glycerol
weight
alumina
process according
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95906988A
Other languages
English (en)
French (fr)
Other versions
EP0742806A1 (de
Inventor
Glyn Roberts
Alan Reginald Minihan
Johannes Arie M. Laan
Johan Jan W. Eshuis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Uniqema BV
Original Assignee
Uniqema BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Uniqema BV filed Critical Uniqema BV
Priority to EP95906988A priority Critical patent/EP0742806B1/de
Publication of EP0742806A1 publication Critical patent/EP0742806A1/de
Application granted granted Critical
Publication of EP0742806B1 publication Critical patent/EP0742806B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C08G65/2657—Aluminosilicates; Clays; Zeolites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives

Definitions

  • the present invention relates to a process of preparing polymers of glycerol in which glycerol, or its derivatives glycidol, glycerol carbonate or isopropylidene glycerol (or 2,2-dimethyl-1,3-dioxolane-4-methanol) are polymerized in the presence of an effective amount of a catalyst.
  • glycerol is condensed at 240°C - 260°C after addition of 0.1-5% by weight of alkali catalyst and the same amount of an aluminium oxide comprising adsorbent.
  • the adsorbent of the aluminium oxide type are activated alumina, zeolite, synthetic adsorbents and activated clays.
  • the zeolite should contain 5% by weight or more of aluminium oxide, but no more indication has been given about the type of the zeolite than that it was manufactured by Mizusawa Kagaku.
  • a catalyst selected from the group consisting of: cesium fluoride impregnated on alumina, potassium fluoride impregnated on alumina, rubidium fluoride impregnated on alumina and zirconium oxide.
  • a catalyst selected from the group consisting of: cesium fluoride impregnated on alumina, potassium fluoride impregnated on alumina, rubidium fluoride impregnated on alumina and zirconium oxide.
  • the alumina on which the RbF, CsF and/or KF has been impregnated is gamma-alumina.
  • the zirconium oxide is preferably zirconium dioxide.
  • the alumina impregnated with rubidium fluoride and/or cesium fluoride and/or potassium fluoride is prepared in a manner known per se, for example as described in Bull. Soc. Chem. Japan 55 (8), 2504-2507 (1982). Also mixtures of rubidium or cesium and potassium fluoride may be used and the amount of fluoride may vary from 0.1 to 1.0 mole of CsF or KF, or more, impregnated on 100 g of alumina.
  • the alumina preferably is gamma-alumina.
  • the zirconium oxide may be zirconium dioxide or the at least partially hydrated zirconium dioxide as may be obtained in a manner known per se. Hydrous zirconia for example is precipitated when solutions of zirconium salts are treated with alkalies. The water is loosely bound and may be removed by drying.
  • the advantage of the use of solid, heterogenous catalysts is that the catalyst can relatively easy be separated from the oligomeric reaction product and that the catalyst can be regenerated. Also the obtained reaction product can at least partially be esterified in the presence of the same catalyst with saturated or unsaturated , straight or branched chain C2-C24 monocarboxylic acids.
  • the present invention relates to a process of preparing polymers of glycerol in which glycerol, or its derivations glycidol, glycerol carbonate or isopropylidene glycerol (or 2,2-dimethyl-1,3-dioxolane-4-methanol) is polymerized in the presence of an effective amount of a catalyst, which is characterized in that the catalyst is selected from the group consisting of rubidium fluoride impregnated on alumina, cesium fluoride impregnated on alumina, potassium fluoride impregnated on alumina and zirconium oxide.
  • the alumina is gamma-alumina.
  • the amount of catalyst used may vary over a wide range from about 0.5% by weight to 100% by weight based on the glycerol, glycidol, glycerol carbonate or isopropylidene glycerol, but preferably from 1% by weight to 10% by weight is used.
  • an inert gas atmosphere may be used, such as a nitrogen blanket.
  • the temperature at which the reaction is effected varies from 150°C to 350°C, although also somewhat lower temperatures may be used. Preferably, a temperature of from 180°C to 250°C is used.
  • a very effective method of heating is the application of microwaves.
  • the reaction may also be favourably influenced by the application of ultrasonic vibrations.
  • the process according to the present invention particularly with cesium-zeolite provides polymerized glycerol having at least 50% by weight, based on the reaction mixture freed from non-polymerized glycerol, of linear oligomers of glycerol.
  • a linear temperature programme was run from 50-275°C at a rate of 5°C/minute with an initial time of 3 minutes at 50°C and a final time of 20 minutes at 275°C.
  • samples were analysed as the silyl derivatives by reacting them with a mixture of hexamethyldisilazane (30 parts) and trimethylsilyl-chloride (15 parts) in pyridine (100 parts) prior to injection.
  • the total amounts do not add up to 100% because the amounts were calculated from the gas chromatography and mass spectrometry.
  • Example II was repeated, but now using 10 grams of cesium exchanged zeolite Y, impregnated with 50% by weight (based on the zeolite) of cesium acetate. The following data were obtained, analysed as described in Example I (in % by weight): Composition after: 19h. 26h. 48h. Glycerol 59 51 31 linear diglycerol 31 35 34 Linear triglycerol 6 10 17 Linear tetraglycerol - 2 7 Linear pentaglycerol - - 3
  • glycerol 51 100 grams of glycerol were heated to 240°C ( ⁇ 5°C) in the presence of 2.5 grams of zirconium dioxide. After 7 hours of reaction, the reaction product was analysed as described in Example I, and its composition was (in percent by weight): glycerol 51; cyclic diglycerol 2; linear diglycerol 28; cyclic triglycerol 2; linear triglcyerol 9 and higher oligomers 5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)
  • Catalysts (AREA)

Claims (8)

  1. Verfahren zur Herstellung von Polymeren von Glycerin, bei dem Glycerin, Glycidol, Glycerincarbonat oder 2,2-Dimethyl-1,3-dioxolan-4-methanol in Gegenwart einer wirksamen Menge eines Katalysators polymerisiert werden, dadurch gekennzeichnet, daß der Katalysator ausgewählt ist aus der Gruppe, die besteht aus Zirkoniumoxid und aus Rubidiumfluorid, Cäsiumfluorid und/oder Kaliumfluorid, imprägniert auf Aluminiumoxid.
  2. Verfahren nach Anspruch 1, bei dem das Aluminiumoxid Gamma-Aluminiumoxid ist.
  3. Verfahren nach Anspruch 1, bei dem das Zirkoniumoxid Zirkoniumdioxid ist.
  4. Verfahren nach Anspruch 1, bei dem die Menge des Katalysators von 0,5 % bis 100 Gew.-%, bezogen auf das Gewicht des Glycerins, Glycidols, Glycerincarbonats oder 2,2-Dimethyl-1,3-dioxolan-4-methanols, beträgt.
  5. Verfahren nach Anspruch 1, bei dem die Menge des Katalysators 1 % bis 10 Gew.-%, bezogen auf das Gewicht des Glycerins, Glycidols, Glycerincarbonats oder 2,2-Dimethyl-1,3-dioxolan-4-methanols, beträgt.
  6. Verfahren nach Anspruch 1, bei dem eine Reaktionstemperatur von 150°C bis 350°C zur Anwendung kommt.
  7. Verfahren nach Anspruch 1, bei dem eine Reaktionstemperatur von 180°C bis 250°C zur Anwendung kommt.
  8. Verfahren nach Anspruch 1, bei dem wenigstens 50 Gew.-% (bezogen auf die monomerfreie Reaktionsmischung) lineare Oligomere gebildet werden.
EP95906988A 1994-02-04 1995-01-24 Herstellung von polyglycerol Expired - Lifetime EP0742806B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP95906988A EP0742806B1 (de) 1994-02-04 1995-01-24 Herstellung von polyglycerol

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP94300859 1994-02-04
EP94300859 1994-02-04
EP95906988A EP0742806B1 (de) 1994-02-04 1995-01-24 Herstellung von polyglycerol
PCT/EP1995/000248 WO1995021210A1 (en) 1994-02-04 1995-01-24 Polyglycerol production

Publications (2)

Publication Number Publication Date
EP0742806A1 EP0742806A1 (de) 1996-11-20
EP0742806B1 true EP0742806B1 (de) 1999-05-06

Family

ID=8217560

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95906988A Expired - Lifetime EP0742806B1 (de) 1994-02-04 1995-01-24 Herstellung von polyglycerol

Country Status (7)

Country Link
US (1) US5723696A (de)
EP (1) EP0742806B1 (de)
AU (1) AU680104B2 (de)
CA (1) CA2180432A1 (de)
DE (1) DE69509497T2 (de)
WO (1) WO1995021210A1 (de)
ZA (1) ZA95632B (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020094254A (ko) * 2001-06-08 2002-12-18 삼광 고하켐 주식회사 불균일 고체산 촉매를 이용한 폴리글리세롤의 제조방법
FR2839067B1 (fr) * 2002-04-25 2006-04-07 Aldivia Nouveau procede d'elimination des peroxydes et de leurs derives d'oxydation presents dans les composes insatures, seuls ou en melange
MY142392A (en) 2005-10-26 2010-11-30 Malaysian Palm Oil Board A process for preparing polymers of polyhydric alcohols
GB0709460D0 (en) 2007-05-17 2007-06-27 Croda Int Plc Method of making polyglycerol esters
US20100125156A1 (en) * 2008-11-14 2010-05-20 Smith Kevin W Condensation reactions for polyols
JP5683115B2 (ja) 2009-01-29 2015-03-11 花王株式会社 ポリグリセリルエーテル誘導体の製造方法
EP2773694B1 (de) 2011-09-28 2016-03-23 Italmatch Chemicals S.P.A. Halogenfreie, flammhemmende polyamidzusammensetzung
WO2013045965A1 (en) 2011-09-28 2013-04-04 Italmatch Chemicals S.P.A. Halogen-free flame retardant polyesters composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1242201B (de) * 1965-11-17 1967-06-15 Basf Ag Verfahren zur Herstellung von niedermolekularen Polyaethern
JPS61238749A (ja) * 1985-04-17 1986-10-24 Nippon Oil & Fats Co Ltd ポリグリセリンの製造方法
JPH01125338A (ja) * 1987-11-10 1989-05-17 Nippon Oil & Fats Co Ltd グリセリン縮合物の製造法
US5349094A (en) * 1992-06-12 1994-09-20 Henkel Kommanditgesellschaft Auf Aktien Process for the production of oligoglycerol mixtures of increased diglycerol content
WO1994018259A1 (en) * 1993-02-10 1994-08-18 Unichema Chemie B.V. Polymerization of glycerol using a zeolite catalyst

Also Published As

Publication number Publication date
US5723696A (en) 1998-03-03
AU1536295A (en) 1995-08-21
AU680104B2 (en) 1997-07-17
WO1995021210A1 (en) 1995-08-10
CA2180432A1 (en) 1995-08-10
EP0742806A1 (de) 1996-11-20
DE69509497D1 (de) 1999-06-10
DE69509497T2 (de) 1999-09-02
ZA95632B (en) 1996-07-26

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